CN105307994A - Bismuth-based glass composition, powder material, and powder material paste - Google Patents

Bismuth-based glass composition, powder material, and powder material paste Download PDF

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Publication number
CN105307994A
CN105307994A CN201480032421.0A CN201480032421A CN105307994A CN 105307994 A CN105307994 A CN 105307994A CN 201480032421 A CN201480032421 A CN 201480032421A CN 105307994 A CN105307994 A CN 105307994A
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powdered material
quality
content
glass composition
composition
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CN105307994B (en
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近藤久美子
加纳邦彦
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Nippon Electric Glass Co Ltd
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Nippon Electric Glass Co Ltd
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    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C3/00—Glass compositions
    • C03C3/04—Glass compositions containing silica
    • C03C3/062—Glass compositions containing silica with less than 40% silica by weight
    • C03C3/064—Glass compositions containing silica with less than 40% silica by weight containing boron
    • C03C3/066—Glass compositions containing silica with less than 40% silica by weight containing boron containing zinc
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C10/00—Devitrified glass ceramics, i.e. glass ceramics having a crystalline phase dispersed in a glassy phase and constituting at least 50% by weight of the total composition
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C3/00—Glass compositions
    • C03C3/04—Glass compositions containing silica
    • C03C3/062—Glass compositions containing silica with less than 40% silica by weight
    • C03C3/064—Glass compositions containing silica with less than 40% silica by weight containing boron
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C8/00—Enamels; Glazes; Fusion seal compositions being frit compositions having non-frit additions
    • C03C8/02—Frit compositions, i.e. in a powdered or comminuted form
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C8/00—Enamels; Glazes; Fusion seal compositions being frit compositions having non-frit additions
    • C03C8/14—Glass frit mixtures having non-frit additions, e.g. opacifiers, colorants, mill-additions
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C24/00—Coating starting from inorganic powder
    • C23C24/08—Coating starting from inorganic powder by application of heat or pressure and heat
    • C23C24/10—Coating starting from inorganic powder by application of heat or pressure and heat with intermediate formation of a liquid phase in the layer

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Chemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Geochemistry & Mineralogy (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Ceramic Engineering (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Dispersion Chemistry (AREA)
  • Glass Compositions (AREA)
  • Other Surface Treatments For Metallic Materials (AREA)

Abstract

This bismuth-based glass composition is characterized by having a glass composition containing, in mass%, 55-80% of Bi2O3, 15-35% of SiO2, 0 to less than 3% of ZrO2, 0-5% of B2O3, and 0 to less than 8% of ZnO, the mass ratio of SiO2/ZrO2being greater than 6.7.

Description

Bismuth glass composition, powdered material and powdered material paste
Technical field
The present invention relates to bismuth glass composition, powdered material and powdered material paste, such as, relating to the bismuth glass composition for forming external coating (EC) on electronic circuit etc., powdered material and powdered material paste.
Background technology
External coating (EC) in order to protect the electrode be formed on soda-lime glass substrate, aluminum oxide substrate etc., resistive element etc., insulating is formed.All the time, in the formation of external coating (EC), use powdered material paste.This powdered material paste is generally the mixture of glass powder and vehicle, sometimes adds ceramic powder as required.
External coating (EC) by powdered material paste is applied to electrode etc. upper after carry out burning till and formed.Wherein, in order to prevent causing the characteristic of electrode etc. that the situation of deterioration occurs because of electrode etc. and the reaction of powdered material, firing temperature is restricted to less than 600 DEG C.Therefore, for powdered material (powdered material paste), requirement can be burnt till under the temperature below 600 DEG C.In addition, for powdered material, also require after burning till, in substrate, do not produce warpage, be not easy to peel off from substrate.
As the powdered material meeting above-mentioned requirement characteristic, up to now, PbO-B is used 2o 3-SiO 2it is glass (with reference to patent documentation 1).
In recent years, from the view point of environment protection, the reduction of carrying capacity of environment material, the reduction of such as PbO are pushed into, and propose various crown glass to replace PbO-B 2o 3-SiO 2be glass.Such as, in patent documentation 2 ~ 4, Bi is described 2o 3-B 2o 3-ZnO system glass.
Prior art document
Patent documentation
Patent documentation 1: Japanese Laid-Open Patent Publication 58-64245 publication
Patent documentation 2: Japanese Unexamined Patent Publication 2009-221027 publication
Patent documentation 3: Japanese Unexamined Patent Publication 2007-63105 publication
Patent documentation 4: Japanese Patent No. 4598008 publication
Summary of the invention
Invent problem to be solved
But, in order to give the characteristics such as non-corrosibility, optical characteristics, mechanical characteristics, electrical characteristic to the electronic circuit being formed with external coating (EC), sometimes implement plating process.In this plating process, external coating (EC) is submerged in plating solution.
Plating solution is generally acidic solution.Therefore, when implementing plating process, external coating needs acid resistance.That is, acid resistance is required to powdered material.
But, the Bi recorded in patent documentation 2 ~ 4 2o 3-B 2o 3-ZnO system glass due to acid resistance low, so have the problem easily being corroded by plating solution, be difficult to maintain the characteristic such as insulativity.
Therefore, the present invention is the invention carried out in view of the foregoing, even if its technical task pioneering also can not to burn till under the temperature less than 600 DEG C containing PbO, be difficult to the warpage of generation substrate simultaneously and be difficult to from the stripping of substrate the bismuth glass composition, powdered material and the powdered material paste that are corroded by plating solution.
For solving the scheme of problem
The present inventor etc. have carried out various experiment, found that, by adopting bismuth glass as glass system, and limit the SiO in glass composition 2and ZrO 2content, above-mentioned technical task can be solved, propose as the present invention.That is, the feature of bismuth glass composition of the present invention is, in mass % containing Bi 2o 355 ~ 80%, SiO 215 ~ 35%, ZrO 2more than 0 and lower than 3%, B 2o 30 ~ 5%, more than ZnO0 and lower than 8% as glass composition, mass ratio SiO 2/ ZrO 2be greater than 6.7.
Usually there is the tendency of acid resistance step-down in bismuth glass, but in the present invention, by by SiO 2content be limited in more than 15 quality % to improve acid resistance.And then the present inventor finds, ZrO 2from as the acid proof composition of raising, but at SiO 2content many when, if ZrO 2content become excessive, then reduce acid proof zircon (ZrSiO when burning till 4) crystallization, be difficult to guarantee desired acid resistance.And then find, bismuth glass is at SiO 2content many when, easily produce scum silica frost etc. when melting, if but when melting zircon crystallization, then the problem such as scum silica frost becomes obvious, and solvability reduces.Therefore, in the present invention, by by ZrO 2content to be limited in lower than 3 quality % and by mass ratio SiO 2/ ZrO 2be limited in more than 6.7, thus suppress the precipitation of zircon crystallization, take into account acid resistance and solvability.
The BaO of bismuth glass composition of the present invention preferably further containing 1 ~ 9 quality %.
The Al of bismuth glass composition of the present invention preferably further containing 0.5 ~ 5 quality % 2o 3.
The content of the content of the preferred MgO of bismuth glass composition of the present invention to be the content of below 5 quality %, CaO be below 5 quality %, SrO is below 5 quality %, and the content of ZnO is below 5 quality %.
Bismuth glass composition of the present invention is not preferably in fact containing PbO.Wherein, " in fact not containing PbO ", although refer to and allow being mixed into the PbO of impurity level, avoids the purport of positive importing, specifically, refers to the situation of content lower than 1000ppm of the PbO in glass composition.
The feature of powdered material of the present invention is, it is the powdered material containing the glass powder be made up of above-mentioned bismuth glass composition and ceramic powder, and the content of glass powder is 50 ~ 100 quality %, and the content of ceramic powder is 0 ~ 50 quality %.
The preferred softening temperature of powdered material of the present invention is less than 600 DEG C.
Powdered material of the present invention is preferred for the formation of external coating (EC).
The feature of powdered material paste of the present invention is, it is the powdered material paste containing powdered material and vehicle, and wherein, powdered material is the powdered material of above-mentioned record.
Powdered material paste of the present invention is not preferably in fact containing phthalic acid based compound.Wherein, " in fact not containing phthalic acid based compound " refers to the situation of content lower than 1000ppm of the phthalic acid based compound in powdered material paste.
Powdered material paste of the present invention is preferably containing one or more in hexanodioic acid based compound, sebacic acid based compound, citric acid based compound.
Embodiment
The feature of bismuth glass composition of the present invention is, in mass % containing Bi 2o 355 ~ 80%, SiO 215 ~ 35%, ZrO 2more than 0 and lower than 3%, B 2o 30 ~ 5%, more than ZnO0 and lower than 8% as glass composition, mass ratio SiO 2/ ZrO 2be greater than 6.7.Below the reason containing scope limiting each composition is as described above described.In addition, at each composition containing in the explanation of scope, % represents and refers to quality %.
Bi 2o 3although be the composition making softening temperature reduce, make the composition that acid resistance reduces.Bi 2o 3content be 55 ~ 80%, be preferably 57 ~ 77%, 60 ~ 75%, be in particular 65 ~ 70%.If Bi 2o 3content tail off, then softening temperature rises inadequately, burns till under becoming the temperature be difficult to below 600 DEG C.On the other hand, if Bi 2o 3many containing quantitative change, then acid resistance becomes easy reduction, and external coating (EC) becomes and easily corroded by plating solution, and result is the protection, the insulation that become the electrode that is difficult to guarantee electronic circuit etc.In addition the surging of material cost is caused.
SiO 2for forming the composition of glass skeleton, and for improving acid proof composition.SiO 2content be 15 ~ 35%, be preferably 17 ~ 33%, be particularly preferably 20 ~ 30%.If SiO 2content tail off, then acid resistance becomes easy reduction, and external coating (EC) becomes and easily corroded by plating solution, and result is the protection, the insulation that become the electrode that is difficult to guarantee electronic circuit etc.On the other hand, if SiO 2containing quantitative change many, then softening temperature rises inadequately, burns till under becoming the temperature be difficult to below 600 DEG C.
ZrO 2for improving acid proof composition.But, at SiO as in the present invention 2content many when, if ZrO 2content become excessive, then zircon crystallization becomes easy precipitation, and acid resistance, solvability become easy reduction.Thus, ZrO 2content be lower than 3%, be preferably lower than 2%, be particularly preferably lower than 1%.
B 2o 3be form glass skeleton, expand the composition of vitrifying scope further, if but they are many containing quantitative change, then and likely acid resistance significantly reduces.Thus, B 2o 3content be 0 ~ 5%, be preferably 0 ~ 4% or 0 ~ 3.5%, be particularly preferably 0.5 ~ 3%.
ZnO is the composition that softening temperature is reduced, but the composition that acid resistance is reduced.The content of ZnO is lower than 0 ~ 8%, is preferably 0 ~ 5% or 0 ~ 4%, is particularly preferably 0 ~ 3%.If ZnO's is many containing quantitative change, then acid resistance significantly reduces, and external coating (EC) becomes and easily corroded by plating solution, and result is the protection, the insulation that become the electrode that is difficult to guarantee electronic circuit etc.
Mass ratio SiO 2/ ZrO 2be greater than 6.7, be preferably more than 7, more than 12 or more than 18, be particularly preferably more than 25.If mass ratio SiO 2/ ZrO 2become very few, then zircon crystallization becomes easy precipitation, and acid resistance, solvability become easy reduction.
Except mentioned component, such as, also can import following composition.
BaO is the composition that softening temperature is reduced, and is the composition making stabilization in addition, particularly suppresses the composition of phase-splitting.The content of BaO is preferably 0 ~ 9%, 1 ~ 9% or 2 ~ 8%, is particularly preferably 3 ~ 7%.If the content of BaO tails off, then glass easily becomes unstable.On the other hand, if BaO's is many containing quantitative change, then acid resistance becomes easy reduction, and external coating (EC) becomes and easily corroded by plating solution, and result is the protection, the insulation that become the electrode that is difficult to guarantee electronic circuit etc.
Al 2o 3be improve acid proof composition, be the composition making stabilization in addition, particularly suppress the composition of phase-splitting.Al 2o 3content be preferably 0 ~ 5%, 0.5 ~ 5% or 0.5 ~ 3%, be particularly preferably 0.5 ~ 2.5%.If Al 2o 3content tail off, then glass easily becomes unstable.On the other hand, if Al 2o 3containing quantitative change many, then softening temperature rises inadequately, burns till under becoming the temperature be difficult to below 600 DEG C.
MgO is the composition that softening temperature is reduced, in addition for making the composition of stabilization.The content of MgO is preferably 0 ~ 5% or 0 ~ 4%, is particularly preferably 0 ~ 3%.If MgO's is many containing quantitative change, then acid resistance becomes easy reduction, and external coating (EC) becomes and easily corroded by plating solution, and result is the protection, the insulation that become the electrode that is difficult to guarantee electronic circuit etc.
CaO is the composition that softening temperature is reduced, in addition for making the composition of stabilization.The content of CaO is preferably 0 ~ 5% or 0 ~ 4%, is particularly preferably 0 ~ 3%.If CaO's is many containing quantitative change, then acid resistance becomes easy reduction, and external coating (EC) becomes and easily corroded by plating solution, and result is the protection, the insulation that become the electrode that is difficult to guarantee electronic circuit etc.
SrO is the composition that softening temperature is reduced, in addition for making the composition of stabilization.The content of SrO is preferably 0 ~ 5% or 0 ~ 4%, is particularly preferably 0 ~ 3%.If SrO's is many containing quantitative change, then acid resistance becomes easy reduction, and external coating (EC) becomes and easily corroded by plating solution, and result is the protection, the insulation that become the electrode that is difficult to guarantee electronic circuit etc.
Except mentioned component, also can import various composition not damaging in the scope requiring characteristic.Such as, in order to make softening temperature reduce, also can import in total amount or separately lower than 5%, particularly lower than 1% Cs 2o, Rb 2o etc.In addition in order to make stabilization, or improve water tolerance, acid resistance, also can import in total amount or separately lower than 10%, particularly lower than 1% Y 2o 3, La 2o 3, Ta 2o 5, SnO 2, TiO 2, Nb 2o 5, P 2o 5, CuO, CeO 2, V 2o 5deng.
In addition, PbO is the composition that softening temperature is reduced, but owing to being also carrying capacity of environment material, so preferably avoid substantial importing.
The feature of powdered material of the present invention is, it is the powdered material containing the glass powder be made up of above-mentioned bismuth glass composition and ceramic powder, and the content of glass powder is 50 ~ 100 quality %, and the content of ceramic powder is 0 ~ 50 quality %.
Glass powder can by such as melten glass is configured as membranaceous after, obtained glassy membrane is carried out pulverize, classification makes.
The median size D of glass powder 50be preferably less than 3.0 μm, maximum particle diameter D maxbe preferably less than 20 μm.If the granularity of glass powder is excessive, then become easy remaining large bubble burning till in film.Wherein, " median size D 50" refer to the value measured with laser diffraction apparatus, represent that, in the cumulative grain-size distribution curve of the volume reference when utilizing laser diffractometry to measure, its cumulative amount is accumulated as the particle diameter of 50% from the side that particle is little.In addition " maximum particle diameter D max" refer to the value measured with laser diffraction apparatus, represent that, in the cumulative grain-size distribution curve of the volume reference when utilizing laser diffractometry to measure, its cumulative amount is accumulated as the particle diameter of 99% from the side that particle is little.
The content of ceramic powder is preferably 40 below volume %, 30 below volume %, 20 below volume %, 10 below volume % or 5 below volume %, is particularly preferably lower than 1 volume %.If ceramic powder is too much, then relatively the ratio of glass powder too tails off, and become and be difficult to form fine and close external coating (EC), external coating (EC) becomes and easily corroded by plating solution.Result is the protection, the insulation that become the electrode that is difficult to guarantee electronic circuit etc.In addition, if add ceramic powder, then the thermal expansivity of powdered material, physical strength, acid resistance can be adjusted.
As ceramic powder, various material can be used, can be added one or more in such as aluminum oxide, zircon, zirconium white, mullite, silicon-dioxide, trichroite, titanium dioxide, stannic oxide etc.
In powdered material of the present invention, softening temperature is preferably less than 600 DEG C, is particularly preferably less than 595 DEG C.If softening temperature is too high, then in order to obtain fine and close external coating (EC), firing temperature must be made to increase, and in this situation, electrode etc. react with powdered material, and the characteristic of electrode etc. becomes and easily deterioration occurs.Wherein, " softening temperature " refers to the value of the 4th flex point measured with large-scale differential thermal analysis meter (DTA).
In powdered material of the present invention, thermal expansivity is preferably 65 ~ 85 × 10 -7/ DEG C, be particularly preferably 72 ~ 80 × 10 -7/ DEG C.Such operation, after soda-lime glass substrate, aluminum oxide substrate form external coating (EC), becomes and easily prevents the warpage of substrate, the stripping of external coating (EC).Wherein, " thermal expansivity " is the value measured in the temperature range of 30 ~ 300 DEG C by thermo-mechanical analysis device (TMA).
The feature of powdered material paste of the present invention is, it is the powdered material paste containing powdered material and vehicle, and wherein, powdered material is above-mentioned powdered material.Wherein, vehicle is for making glass powder disperse and the material of paste, being usually made up of thermoplastic resin, softening agent, solvent etc.
Powdered material paste can by preparing powdered material and vehicle, and by them with the mixing of the ratio of regulation, mixingly to make.
Thermoplastic resin is the composition improving dried film toughness, is the composition giving flexibility in addition.The content of the thermoplastic resin in powdered material paste is preferably 0.1 ~ 20 quality %.As thermoplastic resin, preferred poly-n-butyl methacrylate, polyvinyl butyral acetal, polymethylmethacrylate, polyethyl methacrylate, ethyl cellulose etc., preferably use in them one or more.
Softening agent controls rate of drying, and give the composition of flexibility to desciccator diaphragm.The content of the softening agent in powdered material paste is preferably 0 ~ 10 quality %, is particularly preferably 0.1 ~ 10 quality %.As softening agent, preferably in fact not containing phthalic acid based compounds such as phthalic acid butyl benzyl ester, dioctyl phthalate, phthalic acid di-isooctyl, dioctyl phthalate, phthalic acid dibutyl esters.Such operation, can alleviate carrying capacity of environment.From the view point of environment, as softening agent, the citric acid such as sebacic acid compound, the acetylene tributyl citrate based compounds etc. such as the hexanodioic acid based compounds such as preferred diisobutyl adipate, dibutoxyethyl adipate, Uniflex DBS, sebacic acid two (2-ethyl hexyl) ester, preferably use in them one or more.
Solvent is for making the fat-solvent composition of thermoplastic resin.The content of the solvent in powdered material paste is preferably 10 ~ 30 quality %.As solvent, preferred terpinol, diethylene glycol monobutyl ether acetic ester, 2,2,4-trimethylammonium-1,3-pentanediol mono isobutyrates etc., preferably use in them one or more.
In order to use powdered material paste to form external coating (EC) on electronic circuit, first, on the electronic circuit being formed with electrode, resistive element etc., utilize the coated powder material paste such as silk screen print method, in the lump coating method, after forming the coating layer of the thickness of regulation, make it dry, obtain desciccator diaphragm.Afterwards, by being carried out by desciccator diaphragm burning till for 5 ~ 20 minutes at the temperature of 500 ~ 600 DEG C, the external coating (EC) (burning till film) of regulation can be formed.In addition, if firing temperature is too low, or firing time (hold-time) is too short, then desciccator diaphragm does not sinter fully, becomes to be difficult to be formed fine and close to burn till film.On the other hand, if firing temperature is too high, or the hold-time is long, then electrode etc. react with powdered material, and the characteristic of electrode etc. becomes and easily deterioration occurs.
As the formation method of external coating (EC), to use the method for powdered material paste to be illustrated, but also method in addition can be adopted.Such as also can adopt the methods such as raw cook method, light sensitive paste method, photosensitivity raw cook method.
Bismuth glass composition of the present invention, powdered material and powdered material paste are preferred for the formation of the external coating (EC) of chip resister.In chip resister, aluminum oxide substrate is formed with electrode, resistive element etc., and is formed with external coating (EC) thereon.Further, after formation external coating (EC), the plating process utilizing plating solution is implemented.As described above, even if bismuth glass composition of the present invention, powdered material and powdered material paste be not owing to containing PbO, also can burn till under the temperature below 600 DEG C, and be difficult to produce the warpage of substrate, the stripping from substrate, and be difficult to be corroded by plating solution, so be particularly suitable for this purposes.
Embodiment
Below, based on embodiment, the present invention is described in detail.In addition, the present invention is not by any restriction of following embodiment.Following embodiment is simple illustration.
Table 1 and 2 illustrates embodiments of the invention (sample No.1 ~ 11) and comparative example (sample No.12).
[table 1]
[table 2]
Operate as described below, prepared each sample.First, according to the mode of the glass composition become shown in table, raw material is concocted, mixes equably.Then, to put in platinum crucible and melting, after 2 hours, is configured as membranaceous at 1250 ~ 1350 DEG C.Use the glassy membrane obtained, evaluate solvability.Surface at glassy membrane is not seen devitrification crystallization, the average evaluation of phase-splitting is "○", by seldom seeing devitrification crystallization, the average evaluation of phase-splitting is " △ ", and by significantly seeing pit, the average evaluation of phase-splitting is "×".
Then, after above-mentioned glassy membrane ball mill is pulverized, carry out air classification and obtain median size D 50be less than 3.0 μm, maximum particle diameter D maxit is the glass powder of less than 20 μm.Use the glass powder obtained, evaluate softening temperature and thermal expansivity.
The value of four flex point of softening temperature for measuring with large-scale differential thermal analysis meter (DTA).
Thermal expansivity is formed for each glass powder being carried out pressurization, after burning till at (softening temperature+10) DEG C, be processed into that diameter is 5mm, length is 20mm, after obtaining measuring sample, utilize the value that thermo-mechanical analysis device (TMA) measures in the temperature range of 30 ~ 300 DEG C.
Then, above-mentioned glass powder and vehicle (ethyl cellulose containing 5 quality % and the terpinol of Tributyl O-acetylcitrate containing 3 quality %) are mixed, mixing with triple-roller mill, obtain powdered material paste.And then, in order to obtain about 10 μm burn till film (external coating (EC)), powdered material paste silk screen print method is applied to after on aluminum oxide substrate, coated film is dry, at the temperature of (softening temperature+10) DEG C, burn till 10 minutes with electric furnace, formed and burn till film.Use the band obtained to burn till the substrate of film, evaluate acid resistance.Specifically, after the substrate that band burns till film flood 1 hour in the 5 quality % sulfuric acid of 40 DEG C, carry out washing, after drying, quality measurement reduces, and evaluates the ratio of the Mass lost of dipping front and back.In addition, the ratio of Mass lost is larger, means that acid resistance is lower.
As by table in show, the softening temperature of sample No.1 ~ 9 is low, and solvability, acid resistance are good.Sample No.10 is inclined to, so therefore cause solvability, acid resistance to reduce owing to seldom seeing phase-splitting.Sample No.10,11 is also inclined to, so therefore cause solvability, acid resistance to reduce owing to seldom seeing phase-splitting.The solvability of sample No.12 is bad.
Utilizability in industry
Bismuth glass composition of the present invention, powdered material and powdered material paste are particularly suitable for the formation of the external coating (EC) of formation, the particularly chip resister of external coating (EC), in addition, the purposes such as such as electronic part material tackiness agent, sealing material are also gone for.

Claims (11)

1. a bismuth glass composition, is characterized in that, in mass % containing Bi 2o 355% ~ 80%, SiO 215% ~ 35%, ZrO 2more than 0% and lower than 3%, B 2o 30% ~ 5% and more than ZnO0% and lower than 8% as glass composition, mass ratio SiO 2/ ZrO 2be greater than 6.7.
2. bismuth glass composition according to claim 1, is characterized in that, the BaO also containing 1 quality % ~ 9 quality %.
3. bismuth glass composition according to claim 1 and 2, is characterized in that, the Al also containing 0.5 quality % ~ 5 quality % 2o 3.
4. the bismuth glass composition according to any one of claims 1 to 3, is characterized in that, the content of the content of MgO to be the content of below 5 quality %, CaO be below 5 quality %, SrO is below 5 quality %, and the content of ZnO is below 5 quality %.
5. the bismuth glass composition according to any one of Claims 1 to 4, is characterized in that, in fact not containing PbO.
6. a powdered material, is characterized in that, it is the powdered material of glass powder and the ceramic powder formed containing bismuth glass composition according to any one of Claims 1 to 5, wherein,
The content of glass powder is 50 quality % ~ 100 quality %, and the content of ceramic powder is 0 quality % ~ 50 quality %.
7. powdered material according to claim 6, is characterized in that, softening temperature is less than 600 DEG C.
8. the powdered material according to claim 6 or 7, is characterized in that, it is for the formation of external coating (EC).
9. a powdered material paste, is characterized in that, it is the powdered material paste containing powdered material and vehicle, wherein,
The powdered material of powdered material according to any one of claim 6 ~ 8.
10. powdered material paste according to claim 9, is characterized in that, it is not in fact containing phthalic acid based compound.
11. powdered material pastes according to claim 9 or 10, it is characterized in that, it contains one or more in hexanodioic acid based compound, sebacic acid based compound, citric acid based compound.
CN201480032421.0A 2013-08-09 2014-07-31 Bismuth glass composition, dusty material and dusty material paste Active CN105307994B (en)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
JP2013-165757 2013-08-09
JP2013165757A JP6206832B2 (en) 2013-08-09 2013-08-09 Bismuth glass composition, powder material and powder material paste
PCT/JP2014/070200 WO2015019935A1 (en) 2013-08-09 2014-07-31 Bismuth-based glass composition, powder material, and powder material paste

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CN105307994A true CN105307994A (en) 2016-02-03
CN105307994B CN105307994B (en) 2019-01-15

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CN106517795A (en) * 2016-12-29 2017-03-22 广东羚光新材料股份有限公司 Low-melting-point glass sizing agent and preparation method thereof
CN108470614A (en) * 2017-02-23 2018-08-31 E.I.内穆尔杜邦公司 Chip resistor
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CN113039163A (en) * 2018-11-14 2021-06-25 Ａｇｃ株式会社 Glass substrate for high-frequency device, liquid crystal antenna, and high-frequency device
CN110683764A (en) * 2019-11-15 2020-01-14 黄山市晶特美新材料有限公司 Glass powder for environment-friendly high-acid-resistance automobile glass slurry and preparation method thereof
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